Betaines



United States Patent 3,225,074 BETAINES Frank M. Cowen, NorthPlainfield, N.J., and Gloria Bellis, New Rochelle, N.Y., assignors toAmerican Cyanamid Company, New York, N.Y., a corporation of Maine NoDrawing. Filed Dec. 28, 1959, Ser. No. 862,087 10 Claims. (Cl. 260404.5)

This application is a continuation-in-part of Serial No. 547,845, filedNovember 18, 1955, now abandoned.

This present invention relates to new compositions of matter consistingof betaine derivatives, to the processes of preparing them and to theiruse as germicides.

It has been found that betaine derivatives may be prepared having thefollowing structural formula:

wherein R represents long chain aliphatic hydrocarbon radical containingfrom 10-20 carbon atoms, cycloalkyl, .aryl, aralkyl, or alka-rylradicals; M represents a bivalent radical such as C(=A)D, BC(=A) or--B'C(=A) D in which C is carbon and A, B and D are oxygen, sulfur andimino; R is an alkylene radical (C H containing from 1 to 24 carbonatoms and preferably 1-12 carbon atoms; R and R may represent R M.Rwhere R selected from the group consisting of R and short chainaliphatic hydrocarbon radicals, i.e., alkyl and alkenyl, hydroxyalkyl orR COOMe, wherein x is a whole number from 2 to 4-, y is a number from 1to about 100, R is methyl, ethyl, tolyl or phenyl, and Me is hydrogen,ammonium or a metal, particularly an alkali metal or an alkaline earthmetal; and R is an alkylene radical (C H containing from 1 to 12 carbonatoms and preferably 1-6 carbon atoms.

Typical specific illustrative examples of R are methyl, ethyl, propyl,isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, tert amyl,isoamyl, hexyl, heptyl, octyl, nonyl, decyl, hendecyl, dodecyl,tridecyl, hexadecyl, octadecyl, eicosyl, etc.; allyl, butenyl, pentenyl,hexenyl, oleyl, linoleyl, linolenyl, etc.; phenyl, phenethyl, tolyl,xylyl, methyl xylyl, benZyl, naphthyl, naphthyl methyl, etc.;cyclohexyl, cyclopentyl, etc.

The bivalent radicaltM, represented by the partial formulas andB-C(=A)D-, includes for example, such groupings as aminocarbonylNHC(=O), carbonylamino -C(=O)NH, carbonyloxy -C(=O) O;aminocarbonylamino NH'C(=O)-NH; the corre sponding thio-groupings; andthe substituted imino derivatives wherein the hydrogen of the iminoradical is substituted by alkyl, cycloalkyl, alkenyl, aryl, aralkyl andalkaryl groups.

Representative examples of radicals R and R are methylene, ethylene,propylene, butylene, pentamethylene, etc., with the range of carbonatoms being from 1 to 24 and from 1 to 12, respectively.

The hydroxyalkyl radical may be illustrated by such examples ashydroxymethyl, hydroxyethyl, hydroxypropyl, ect. Similarly, the (C H R'H radical may be illustrated by such examples as ethenoxy, diethenoxy,dipropenoxy, triethenoxy, tetraethenoxy, pentaethenoxy, octaethenoxy,octadecaethenoxy, phenylethenoxy, etc. In the hereinafter describedillustrative examples, it is to be noted that ethylene oxide is the mostcommonly used 3,225,074 Patented Dec. 21,. 1965 oxide but such has beenthe case primarily for illustrative purposes and is not to be construedas limitative ofthe' invention. Consequently, other alkylene oxides suchas propylene oxide and isobutylene oxide, as well as styrene oxide maybe used.

The radical Me may be hydrogen, ammonium or a metal such as sodium,potassium, magnesium, calcium, etc.

The betaines of the present inventionare prepared by initially makingintermediate products suitable for conversion to the desired betaines.These intermediate products include, for example, (1) tertiary aminescontaining amide groupings resulting from the reaction of an acid(including thionic acids) and an aminoalkyl-substituted tertiary amine;(2) tertiary amines containing amide groupings resulting from thereaction of an acid (including thionic acids) and anaminoalkyl-substituted secondary amine, followed by further treatment ofthe reaction product with an alkylene oxide; (3) tertiary aminescontaining ester groupings resulting from the reaction of an acid and analkanolamine containing a tertiary amine grouping; (4) tertiary aminescontaining amide groupings resulting from the condensation of ureaand'N-substituted ureas with a diamine containing one tertiary aminegrouping, etc.

These tertiary amine-intermediate products are then reacted with anomega-halogen-substituted aliphatic acid, such as a-chloracetic acid,fi-chlorpropionic acid, 'y-chlorbutyric acid, etc., in the presence ofan alkaline material, such as an alkali metal or alkaline earth metalhydroxide, to form the desired betaine.

The above compounds and radicals have been cited as illustrative of thematerials which can be used in the present invention and it is to bepointed out that such is not to be construed as limitative of theinvention, but that corresponding and equivalent compounds and radicalsmay be used within the spirit of the inventive concept.

The invention will be further illustrated in more specific detail by thefollowing examples. It should be understood, however, that althoughthese examples may describe in. more particular detail some of the veryspecific features of the invention, they are given primarily for,purposes of illustration and the invention in its broader aspects isnot to be construed as limited thereto.

Reactants Mole (s) Gms.

Acintol fatty acid 1 1. 0 Bis-(3-aminopropyl)methylamine 0. 525

The acid (Acintol Fatty Acid 1 is a fractionated mixture of tall oilfatty acids and contains about 48% oleic acid, 43% linoleic acid andabout 3% saturated acids) and the amine were added along with xylene asan entraining agent to a 3-neck flask'fitted'with a thermometer,stirrer, water trap and reflux condenser. The mixture was heated atreflux for about seven hours at -195 C. At the end of this period, thetheoretical amount of water (1.0 mole) had collected in the water trap.A sample was titrated and found to contain less than 1% uncombinedcarboxylic acid. It was therefore stripped free of xylene and unreactedamine and used directly for the preparation of the betaine. Yield, 97%.

Example 2.N,N-bis-(oleylamidopropyl)-amine ITHi-asCONHCHzCHg'CHz HCHEM-33C ONHCHgCHgCH 4. fat 11 is a mixture of fatty acids obtained byfractional distillation processes and comprises 90% lauric acid, 9%myristic acid and 1% oleic acid.)

PREPARATION OF INTERMEDIATE ESTERS Example 8.N-stear0yl0xyethyl-N,N-bis-Reactants Mole (s) Gms. 6 I amine 0 A t lFAl 1.5 441 l Bi s- 3amin0pr0pyl)-amine 0.788 103 10 OUHHAOCLDCEE /CH2CH2OH N By theprocedure in Example 1, the mixture was heated \CHZCHZOH for 11 hours at145-195 C. Stripping gave a 98% yield of product. 15 Reactants M0le(s)Gms.

Example 3.N,N-bis-(stearamidopropyl)-N- melhylllmine Hydrofol 40s- 1. 021; C15-11H31 35CONECHQOHQCH; CH3 Tnethanommme' l Similar to Example 5but heated for four hours at 150 CIWHMECONHCHNHQCH 195 C. A light tanwax was obtained in a 90% yield.

Reactant M01) Gms Example 9.N,N-bis-(stear0yl0xyethyl)-N- S(Z-hydroxyethyl) -amine Hydroiol 495 1.0 277 25Bis-(3-aminopropyl)-Inethy1amine 0.525 76 Reactants Mole(s) Gms.

Hydrofol 405 is a commercial grade of stearic acid" l 'ly a loli0i 1 2;;and contains about 65% stearic acid, 28% palmitic acid, m mm mmm 2%myristic acid and 6% oleic acid. After heating for 30 six hours at152189 C. and stripping, the product yield Heating for eleven hours at141l90 C. by previous was 97%. It set to a hard yellow wax. methods gavea tan wax, 96% yield.

Example p py m Example 10.N,N-bis-(stearoyloxyethyl) -N- methylamineReactants Mole(s) Gms.

Reactants I Mo1e(s) Gms. Hydrofol 405 1. 3 360 Bis-(B-aminopropyD-ainine0. 683 89 Hydrofol 405 i. 0 277 Diethaiiolmethylamine .a 0. 5 61 Heatingfor ten hours at 183185 C. and stripping 40 gave a 100% yield of theamide. a

A similar preparation in which nitrogen gas was subth Thirteen hours at135 160 gave a 100% yield of stituted for xylene gave a quantitativeyield after sixteen es hours at PREPARATION OF INTERMEDIATE TERTIARYExample 5 .N,N-bis-(stearamidoisopropyl) -amz'ne AMINES(HYDROXYETHYLATION) Example 11.N,N-bis-(0leylamid0pr0pyl)- ReactantsMole(s) Gms. hydrOxyethylaml-ne Hydr0fo1405 1. 0 277 011E330 C 2 Hz 2CHzCHzOH Dipropyleiie triamine 0.5 67 \N/ 0 711330 ONHCIIzCI-IgCfizEmploying both nitrogen and xylene, a 96% yield was obtained aftertwenty-two hours at 147l84 C.

Reaetants Equivalents Gms. Example 6.N,N-bzs-(stearamzdo ethyl)-amzne N,N-Bis-(oleylamidopropyD-amine (Ex. 0. 4 281 Re ct nts V I Mo1e(s) Gms.Ethivlene oxide 19 Hydrof01405 1.0 277 Diethylenetriamine 0.5 57 60 Theamide was dissolved in 300 g. of isopropyl alcohol and treated with theethylene oxide for 1.6 hours at 78- Similar to Example 5 but heated forsix hours at 165 P gave the hydroxyethylated Product 173 Yield, inquantitative yield.

Example 7' N laummidopmpyLNALdimethy[amine Example J2.-N,N-bis-(stealamidopropyl)-hyaroxyethylamzne Reactants M0le(s) I Gms.

Reactants Equivalents Gms. Neoiat ii 1.5 3103-dimethylamiriopropylainine H 1.875 191N-N-bis-(stearaiiiidopropybamiiie (Ex.

4) 0.65 421 Ethylene oxide 29 Similar to Example 5 but benzenesubstituted for xylene OPYI alcohol 420 and only 25% of amine added atstart. Rest added dropwise over a seven hour period. Total heating timewas twenty-eight hours at 113l64.5 C. Yield, 98%. (Neo- Example13.-N,N-bis-(stearamidoisopropyl)-hydrxyethylamine Reactants EquivalentsGms.

N,N-bis-(stearamidoisopropyD-amine Ex. 0.5 298 Ethylene oxide- 21.Isopropyl aleoho 237 Treated for 2.3 hours at 50-90 C. Quantitativeyield of hydroxyethylated product.

Treated for 2.8 hours at 6780 C. Quantitative yield.

PREPARATION OF BETAINES Example 15.N,N-bis(oleylamidopropyl)-N-methyl-N- carboxymethylammonium betaine C 7H33C ONHCHZCHZCEZ CH3CnHuC ONHCHzCH CHz CHzCOO- Reactants Equivalents Gms.

N,(I] -bis)(oleylamidopropyl)Nmethylamine 279.

Chloracetic acid Sodium hydroxide Eth an 01 Water 50 ml. 75 ml.

The chloracetic acid was suspended in the water in a flask of suitablesize equipped with a stirrer, thermometer, and reflux condenser. Theacid was neutralized with the sodium hydroxide as a 40-50% aqueoussolution while cooled in an ice bath. The amine in alcohol was added andthe mixture refluxed for five hours.

At the end of the reaction the mixture was diluted with alcohol andevaporated to dryness. The resulting solid was dissolved in benzene andthe insoluble salt (sodium chloride) removed by filtration. The filtratewas evaporated to dryness to give a brown paste in quantitative yield.

The product was useful as a germicide and killed 24- hour cultures ofSalmonella typhosa in 10 minutes at C. in dilutions up to 1:1000.

It was also useful as a softening agent for textiles, particularlycottons.

It is to be noted that the R MR -grouping in Example 15 is, in eifect,an alkenylamidoalkyl radical, as

(Example 33), or the thio-substituted alkylcarbamylaminoalkyl,alkylamidoalkyl and arylamidoalkyl radicals (Examples 34, 35, 36).

6 Example 16.-N,N-bis-(oleylamidopropyl)-N,N-bis(carboxymethylammonium)betaine, monosodium salt 0 E 0 ONHCHzCHzOHz cat000- 0 E 0 ONHOHROHZOHQOH C OO-.Na+

Reaetants Equivalents Gms.

N ,N-bis-(oleylamidopropyD-amiue (Ex. 2)- 0. 25 176. Chloracetic acid 0.50 Sodium hydroxide O. Eth an 01 35 1111. Water 75 ml.

Reflux for six hours and workup gave a quantitative yield of viscousbrown liquid.

Example 1 7.N,N-bis- (stearamidopropyl -N-methyl-N-carboxymethylammonium betaine o 1 m oomro H2O mom CH3 ReaetantsEquivalents Gms.

Nag-big;(stearamidopropyl)-N-methylamine 0. 50 292.

x. Chloracetic acid 0. 50 Sodium hydroxide 0. 50 Ethanol m1. Water 50ml.

A reflux time of five hours and usual work up gave a yellow wax(quantitative).

The product was useful as a cotton softener. It was also useful as agermicide and killed 24-hour cultures of Salmonella typhosa in 10minutes at 20 C. in dilutions up to 1:1000.

Example 1 8 .-N- (stearamidopropyl N ,N -dimethyl-N-ca'rboxymethylammonium betaine Five hours refluxing and workup gave aquantitative yield of a white Wax. The product was useful as a detergentand as an anti-static agent.

Example 19.N,N-bis-(oleylamidopropyl) -N-(2-hydr0xyethyl)-N-carb0xy-methyl ammonium betaine 0 E 0 ONHCH CHaCHz OH CI-I OHC17H3QCONHCH2CH2CH2 011 000- Reactants Equivalents Gms.

N,N-bis-(oleylamidopropyl)-N-(2-hy- 0. 20 300 (ineludingdroxyethyD-amine (Ex. 11). isopropyl alcohol). Chloracetie acid Sodiumhydroxide.. Isopropyl aleohol 30 rnl.+. Water 40 ml.

Refluxing for five and three-quarter hours and recovery gave a viscoussticky brown paste in quantitative yield.

Example 20.N,N-bis-(stearamidopropyl)-N-(2-hydroxyethyl)N-carboxy-methylammonium betaine I 17 35C ONHCH2CHz Hz CHzC O O- Rcactants I EquivalentsI N,N-bis (stearamidopropyl)-N- (2-hydroxyethyD-amine (Ex. 12).

Chloracetic acid Sodium hydroxide Gms.

0. 65 870 (including isopropyl alcohol).

A quantitative yield of tan or brown wax was obtained after about sixhours of reflux and recovery.

Example 2] .N-stearyloxyethyl-N,N-bis-(Z-hydroxyethyl)-N-carboxymethylammonium betaine C H3 C 0 O OHQCH CH CH2OH CH;CH2OH CH CO o- RcactantsEquivalents Gms.

N-stearoyloxyethyl-N,N-bis-(2-hydroxy- 0.286 200.

ethyD-amine (Ex. 8).

The refluxing time was six and three-quarter hours. The product wasuseful Quantitative yield of tan Wax. as a detergent and anti-staticagent.

Example 22.N,N-bis- (stearoyloxyethyl) -N-(2-hydroxyethyl)-N-carboxymethyl ammonium betaine CnHuCOOCHzCHg CHzCH2OH C11H35COOCH2CH:0112000- Reactants Equivalents Gms.

N,N-bis-(stearoyloxyethyl)-N-(Z-hydroxy- 0086 200.

ethyD-arnine (Ex. 9).

Ohloroacetic acid 0. 086 Sodium hydroxide 0. 086 Ethanol 150 ml. Water40 ml.

8 Example 24.N,N-bis-(stearamidoisopropyl)-N-(2-hydroxyethyl)-N-carboxymethyl ammonium betaine 611E 0 ONHOH2CH CHZCHZOHC11H35CONHCH3CH CHZCOO I O Reactants Equivalents Gms.

N ,N-bis(stearamidosiopropyl)-N-(2- 0.50 560 (including hydroxyethyD-ane.

isopropyl alcohol).

100 ml.+. 75 m1.

Seven hours refluxing gave an orange-brown paste. Recovery wasquantitative.

Example 25.-N,N-bis- (stearamia'oethyl) -N- (Z-hydroxyethyl-N-carboxymethyl ammonium betaine C17H35CONHCHZCH2 CHzCHzOH 01711350ONHCHzCH-z CHZCOO Rcactants Equivalents Gms.

N,N-b1s-(stearam1doethyD-N-(Z-hy- 0.493 555 (including droxyethyD-amine.isopropyl alcohol). Chloroacetic acid 0. 493 Sodium hydroxide. 0. 493Isopropyl alcohol ml. Water 150 ml.

A reflux time of five hours and workup gave a quantitative yield of atan Wax.

Example 26 .N,N -bis-(stearoyl0xyethyl -N -methyl-N-carboxy-methylammonium betaine C17H35COOCH2CH: CH3

(31 113 0 0 O CHzCHz CH COO Reactants Equivalents Gms.

Chloroacetic acid Sodium hydroxide Isopropyl alcohol Water N,N-bis-(stearoyloxyethyl) -N-methylamine Six and three-quarter hours refluxgave a 92% yield of tan wax.

Example 23.-N,N-bis-(N'-stearylpropionamide)-N-(2- hydroxyethyl)-N-carboxymethyl ammonium betaine Reactants Equivalents Gms.

N,N-bis-(N-stearylpropionamide)-N-(2-hy- 0.071 72.

droxyethyD-amine.

Chloroacetic acid Sodium hydroxid Ethanol ml. Water. 40 ml.

A refluxing time of seven hours resulted in the recovery It possessed ofa quantitative yield of a brown utility as a textile softener.

WaX.

Seven and one-quarter hours Was suflicient reflux time to give a 94%recovery of a tan wax product. It was useful as a cotton softener.

Example 27.N-(lauramidopropyl) -N,N-dimethyl-N- Example 28.Plyethyleneglycol product C17H35OONHOH2CH2OH2 /CH2CH2O (CHzCHzOM-eI-ICuHuCONHCHzCHzCHz CHzCOO" Reactants Equivalents Gms.

Betaine in Ex. 19 0. 1 88 Ethylene oxide Isopropyl alcohol 111 *Actulalyreacted. Excess used.

The betaine was dissolved in the alcohol, the mixture heated to 20 C.and ethylene oxide added at 6278 C. for 2 /3 hours. The final product, apolyethenoxy derivative obtained in quantitative yield, was a brown 47%solution.

This material contained 2.6 mols of combined ethylene oxide for each molof the original betaine. It was therefore a mixture of two or moreethylene oxide condensation products.

Example 29.Polyethylene glycol product CnHsaCONHCHzCHzCHz GHgCHzO(CH2CHzO)3uH N C17H35CONHCH3CH2OH1 CHzC O O" Reactants Equivalents Gms.

Betaine in Ex. 19 0. 1 88 Ethylene oxide *3. 0 Isopropyl alcoh nl 111*Actually reacted. Excess used.

The betaine was dissolved in the alcohol, the mixture heated at 20 C.(under 100 psi.) and ethylene oxide added at 6278 C. for 7 hours. Thefinal product, a polyethenoxy derivative, was obtained in substantiallya quantitative yield. It was useful as an emulsifier.

Example 30.N,N-bis(propylamid0propyl) -N- methylam z'neC3H7CONHCH2OH2CH2 CH N C3H7C ONHCH2CH2CH2 Reactants Mole (s) Gms.

Propionic acid 1 74 Bis-(3 aminopropyl)-methylamine 0. 525 76 Theprocedures set forth in Example 1 were followed substantially as setforth therein. The yield was quantitative.

N,N-bis(propylamidopropyl)-N-methyl-N- carboxymethyl ammonium befaineC3H7CONECH2CH2CHI C Ha The procedures of Example 15 Were followed, usingsubstantially equal molal amounts of amine, chloracetic acid and sodiumhydroxide. The yield was quantitative.

Example 31.N,N-bis(dodecylbenzylamidopropyl)-N- decylamineC12H25C6H4CONHCH2CH2CH2 /CH21 Reactants Mole (s) Gms.

p-D odecyl benzoic acid 1 293 Bis-(3-amin0p10pyD-decylamiue 0. 525 184Using cyclohexyl carboxylic acid and bis-(3-aminopropyl)-octylamine toform the intermediate tertiary amine and chloracetic acid and sodiumhydroxide to form the betaine.

Example 33 Using N-dodecylurea and 3-aminopropyldimethylamine in theformation of the tertiary amine, followed by its reaction withchloracetic acid and sodium hydroxide in the formation of the betaine.

Example 34 CH3 ownz mrcsunoazomona r omo 0 0- Using N-dodecyl thio-ureaand 3-aminopropyldimethylamine in the formation of the tertiary amine,followed by its reaction with chloracetic acid and sodium hydroxide inthe formation of the betaine.

Example 35 r oimo ONH(CH2)12N+CHQCOO- Using butyric acid anddimethylaminolaurylamine to form the tertiary amine and chloracetic acidand sodium hydroxide to form the betaine.

Using ethanethionic acid and a slight excess of3-dirnethylaminopropylamine in the formation of the intermediatetertiary amine and chloropropionic acid and sodium hydroxide in theformation of the betaine.

Using thiobenzoic acid and a slight excess of 3-diethylaminopropyl inthe formation of the intermediate tertiary amine and chlorobutyric acidin the formation of the betaine.

The products of the present invention were determined to be useful asgermicides. One specific evaluation of a particular product is set forthbelow as illustrative of such utility. The product wasN-(lauramidopropyl)- N,N-dimethyl-N-carboxymethylammonium betaine(Example 27) used on a 35% solids basis and the test procedure used wasthe EDA. method described in Circular #198, United States Department ofAgriculture. The

test organism was a 24-hour culture of Salmonella typhosa (Hopkins) andthe incubation period was 48 hours at 370 C. The following tableindicates the results obtained.

TABLE I Evidence of growth after mins. mins. mins.

Concentration of betaine:

Legend: +indicates growth; indicates no growth.

As a control and comparison, a similar test procedure was used on asolids solution of stearamido-propyldimethyl B hydroxyammoniumdihydrogen phosphate (SP). This product (SP) is not a product of thepresent invention but was selected as it bears some structuralresemblance to the products of the present invention. The followingtable indicates the results obtained.

Legend: +indicates growth; indicates no growth.

The above tables indicate that a 1:1500 dilution of the betaine killed a24-hour culture of Salmonella typhosa in 10 minutes at a temperature of20 C. This corresponds to a 1:85 dilution of phenol. The phenolcoeflicient is therefore 180.1. With regard to product SP, the 24-hourculture of Salmonella typlzosa was killed in 10 minutes at 20 C. with adilution of 1:25. This corresponds to a 1:85 dilution of phenol. Thephenol coefiicient is therefore 0.3.

Although we have described specific examples of our inventive concept,we consider the broad aspects of the same not to be limited to thespecific substances mentioned therein but to include various othercompounds of equivalent function and constitution as set forth in theclaims appended hereto. It is understood that any suitable changes,modifications and variations may be made without departing from thespirit and scope of the invention.

We claim: 1. Betaines having the formula Rs 31.0 O.NH.Rz-l T Rs-C oowherein R is an aliphatic hydrocarbon radical of from 10 to 20 carbonatoms selected from the group consisting of long-chain saturatedaliphatics and long-chain alkenyl aliphatic radicals, R and R arealkylene radicals of from 1 to 12 carbon atoms, R is a member of thegroup consisting of C H in which n is a whole number from 1 to 10 and CH .OH in which n is a whole number from 1 to 3 and -(C H .O) H in whichx is a whole number from 2 to about 100, and R is a member of the groupconsisting of R R CO.NH.R

and R COOMe in which R R R and R are as defined above and Me is amonovalent salt-forming radical.

2. N,N bis(oleylamidopropyl)-N-methyl-N-carboxymethylammonium betaine.

3. N,N bis(oleylamidopropyl) N,N bis(carboxymethylammonium) betaine,monosodium salt.

4. N,N bis (stearamidopropyl) N methyl N- carboxymethylammonium betaine.

5. N (stearamidopropyl) N,N dimethyl N carboxymethylammonium betaine.

6. N,N bis (oleylamidopropyl) N (2 hydroxyethyl)-N-carboxymethylamm0niumbetaine.

7. N,N bis (stearamidopropyl) N (2 hydroxyethyl)-N-carboxymethylammoniumbetaine.

8. N,N bis (stearamidoisopropyl N (2hydroxyethyl)-N-carboxymethylammonium betaine.

9. N,N bis (stearamidoethyl) N (2 hydroxyethyl)-N-carboxymethylammoniumbetaine.

10. N (lauramidopropyl) N,N dimethyl N carboxymethylammonium betaine.

References Cited by the Examiner UNITED STATES PATENTS 2,504,427 4/ 1950Kilgore 16722' 2,777,872 1/ 1957 Shacklett 260-501 2,781,385 2/1957Spivack et al 260-404.5 2,875,219 2/1959 Huber et a1. 260-4045 2,924,5522/ 1960 Harwood et a1. 167-22 2,935,493 5/1960 Schuller et al. 260501OTHER REFERENCES Bergmann, The Chemistry of Acetylene and RelatedCompounds, 1948, page 80.

CHARLES B. PARKER, Primary Examiner. A. H. WINKELSTEIN, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,225,074 December 21, 1965 Frank M. Cowen et al.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 1, line 12, for "This" read The line 43, for "tert amyl" readtert-amyl column 3, lines 21 to 28, in the table, first column, line 1thereof, for "Hydrofol 495" read Hydrofol 40S column 8, lines 9 to 18,in the table, first column, lines 1 and 2 thereof, for "N,N-bis(stearamidosiopropyl) N-(Z-hydroxyethyl] amine" read N,N-

bis[stearamidoisopropyl) N-(Z-hydroxyethyl) amine column 9, line 12, for"Actulaly" read Actually column 10, line 12, for "N-carboxylmethyl", initalics, read N-carboxymethyl in italics; column 11, line 3, for "370C." read 37 C. line 48, for "180.1" read Signed and sealed this 20th dayof December 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. BETAINES HAVING THE FORMULA